YISCOSITT OF zIQL-EOI-S SOLI-TIOSS OF STJLFALIIC

T H E RELL4TIT7E
ACID *IXD OF SOME OF ITS S-iLTS .1T 25°C.
-1. F. SCHMELZLEI ASD J. E.JTESTFALL2
Department 0.f Chemistry, T h e Creighton Cnitersity, Omaha, Sebrasha

Recewed M a r c h 18, 1944

The solubility in \\ ater of the barium, calcium, and magnesium salt, of sulfaniic
acid has recently heen reported by King and Hooper (3). In vieTv of the in-
creased use of suliamic acid and of its salts, it qeenii desirable that more data
concerning the p h p i m l propertiei of Its solutions be available. I t is the purpow
of this investigation to determine the T iscosity mid the density of -olutioni
of sulfamic acid arid of the ammonium, barium, calcium, and magnesium ialts
of this acid.
EXPERIJICST.1L

Sulfamic acid of iwgent grade, purchased from the G. Frederick Smith Chemi-
cal Company, was recrptallized from water, dried in air, and stored over Anhy-
drone The barium, calcium, and magnesium salts were prepared by treatment
of a solution of the Icagent-grade acid n-ith a slight excess of a C . P . grade of the
carbonate of the desired metal (3). The ammoniuni sulfamate was prepared by
two recrystallization- of a technical grade of the salt from water.
Two viscometers of the Ostwald type irere employed for each determination.
They n-ere rigidly m y e n d e d in a constant-temperature water bath regulated a t
25.00"C. f 0.04". Ai pipet was used to introduce the same volume of solution
into each viscometer for the different trials. Xll solutions were prepared with
water filtered through sintered-glass filters. An interval of 15 to 30 min. wis
allowed for temperature equilibrium. The rate of flo~vwas timed n-ith a stop
watch reading to 0.2 sec. From three to six readings n-ere taken for each trial,
and the average of these readings was recorded as the time of flow. -After each
run, the viscometrrs were cleaned n-ith chromic acid cleaning solution and then
rinsed successivell- with filtered water, alcohol, and ether. They Trere dried
by a current of filtered air.
Calibrated pycnometers were used to determine the densities. &illTreights
were corrected for the buoyancy effect of air.
RES'CLTS AND DISCCSSIOS

The data for the various solutions are given in tables 1, 2,3,4, and 5 , in n-hich
the first column gives the concentration, C, in gram-equivalents of solute per
liter of solution, the ,qecond column gives the density, d , in grams per milliliter
of solution relative to that of water a t 4"C., and the third column lists the relative
viscosity, B I B o .
Present address: 11innesota 11ining and Manufacturing Compnny, St. Paul, LIinnesota.
Present address Glenn L. Martin-Sebraska Company, Omaha, Sebraska.
165
 T.1BLE 1
17iscocl't:/ cj' stiljciniic a c i d soltitions
~________~~_____ .

~' c 1

1
i' d '7 '7, 9
1
i!
______ ~ _ _ _ ____._~
. ~ ~ _ _ , -
0.1303 1.0034 ~ 1.0161 I' 0.6736 1.0:319 ' 1.0644
0.17YE 1.0064 0.7331 1.0331 1 1.0707
;:g;
,
~

0.2579 1.0103 0.9603 ~ 1.0466 1.0902

0.3773 1.0166 1 ,0349 1.1951 1.0587 1.1145
0.4676 ~ 1.0214 1.0450 , 1 ,6445 1 .os11 1.1668
0.4974 ~ 1.0229 1.0551 I' 2.0724 1.1025 1.2214
I1 .. .~
..

T.iBLE 2
V i s c o s i t y of rnngnesiiitn sulfamate solzittons
- -
c I d I c <I

0.0422 0.9995 1.0139 li 0.6582 1.0479 1.2003

0.0866
0.1696
0.2506
0.3992
0.5366
1

,
1,0034
i.on99
1.0158
1.0258
1.0372
1 0210
1.0487
1 0643
1.1059
1.1551
1
1 0.8042
1 ,0238
1.5082
2.7160
4 4960
1.0571
1.072s
1.1072
1.1917
1,3106
1,2393
1.3160
1.4940
2.1960
4.4660

TABLE 3 i
T-iscosity of b a r i u m sulfamate solutions

0.05ss 1 ,0082 1 ,0831 1.1501

0.1012 1,0107 0 9654 1,1179 1,2024
0.1980 1.0220 1 ,2334 1.1299 1 ,2334
0.3992 1.193G 1.3775
0.5866 1,0715

TABLE 4
T'iscosity oj calcz~inrsulfamate solutions
_ _
C d 9 'io I' c d rl 9 )
I
_______
0.0629 1.0014 1 .O140
-
1
I- 0.7029 1.0321) 1.1580
0.0626 1.0051 1.0275 '1 0.7258 1 ,0594 1.1711
0.1615 1.0169 1.0448 11 1.0130 1.0740 1.2310
0.2209
0.3432
1,0148
1.0248
1.0502
1 . OS26 '1~ 1.4611
2.0S76 ,
1 1.1207
1.1690
1.4060
1.6674
0.4657
0.4715
0.6014
1

,
1 ,0336
1 ,0372
1.0454
1.0991
1 . ODs2
1,1378
'
I1
2.6746
3.4820 1
I
1.21Yh
1,2771
1.9616
2.5946
I,
 SOLUTIOSS O F SULF.i>lIC ACID - i S D O F h U L F . U I I T E S 16'7

Gruneisen (1) noted that a plot of (v/lvo - l ) ; C against C passed through a

miniinurn a t a lon- concentration for solutions of electrolytes. Jones and Dole

TABLE 5
1-iscosit y of a niinoi1 i z i m s u l f a mate sol ii t io ii s
c I ? '70 C d
-

0.1185 1.0030 1 .0054 1 .S263 1,0902 1.119s

0.20i4 1.0091 1 ,0054 1.9127 1.0946 1,1226
0 . 2958 1.0125 1.0188 3.4105 1.1659 1.3136
0 . AT65 1.02lb 1 ,0244 5,0832 ~ 1.2435 1.6iOS
0.6863 1.0310 1 ,0334 6.3656 1.3011 2.1874
0.8254 1 ,0404 1,0426 T.1S13 , 1.3402 2,7543
1 .0245 1 0504 1.0813 I' S . 1696 1.3830 3.8298
1.2778 I ,0632 1 ,0734

TABLE 6
C'orcstarzts o j the J o n e s arid Dolc equalton
_____ . .

snLI TI A R DEI IATICJ\

pcr ceizt

HPO9SH: -0.0087 -0. 0801 0.215

31g(dOaSH~): -0 0130 - 0.2265 0.378
Rn(SO3SH:I: -0.0126 -0,1541 0.507
Ca(SOJSHJI -0.0380 -0.14S4 0.371
SHaS03SHz f 0 ,0051 -0.0556 0.202

TABLE T
Consfants of t h e Root e q u a t i o n
~~ _ _ _ _ - ~

SOLLIE Ki I\? DE\I4TIO\

__ ~ --_____
I I pei cenl
HSOiSHz 0.0501 $0 .000863 0.263
lIg(S03SH,), 0.0716 +0 000769 0.205
B~(SO~SH?)L 0 1390 - 0.01 76 0 321
C a (S03SHz) , 0.0918 -0.00i8i 0.339
SH,SO3SHA 0.0540 -0.00238 0.058
- I __

(2) found that thi. relation can be expreqsed in terms of the fluidity of the solution
by an equation n-hich may be n-ritten in the follon-ing straight-line form :

TT here -1 and B nie (lonqtants characteriqtic of the electrolyte. plot of' p -

I / & against v foi a nuinher oi yolutions yielded n 5traight line for concentra-
tions lip to aliout 1 normal. This equation na. npplietl to the data ohtained for
168 GRAST W. SMITH

the sulfamic acid and sulfamnte .mlutions to a concentration of 1 normal, and the
constants er-aluated by the nietliod of least squares. Table cj lists the values
of these constants and also the average percentage der-iation of the calculated
fluidities from the observed vnliies.
The densities of the solutions studied may lje expressed in terms of the Root
(4) equation, rrhich may be w i t t e n

d-
c do = Kl + K22/C
in nhich do is the den-ity of pure \later, and Iil and li2are constants. The
values of theie constant-. together \\ ith the average percentage deviation he-
tween the calculated densitie- and tho-e obseived foi thc wlfamic acid and
sulfainate qolutions, are given in table 7 .

scmr.mx-
1. The relative Yiscosity and the relative density of solutions of sulfamic acid
and of the ammonium, barium, calcium, and magnesium salts of sulfamic acid
h a r e been studied over the range of the solubility of these substances in water.
2. The results may be espressed by the Jones and Dole equation for fluidities
up t o 1 normal and by the Root equation for densities over the entire concentra-
tion range studied.
REFERESCES
(1) GRUSEISES,E.: Wiss. .\blinndl. physik-tech. Reichnnstalt 4, 2.77 (1905).
( 2 ) JOSES,
GRISNELL,ASD DOLE,~ I . \ I ~ c o LJM . -:h i . Cheni. S O C61,
. 2950 (1929).
(3) KISG, G. R., A X D H O O F E RJ.. F . : J. Phys. Cheni. 46, 038 (19411.
(4) ROOT,W. C.: J. h n i . Cheni. SOC.66, 850 (1933).

THE 3IEASURElIEST OF BOUSDARY T E S S I O S BY THE

P E S D E S T - D R O P I I E T H O D . I1
HTDROCARB
OS s

GRAST W , SMITH'
Department of ChenizstrU, 1 he I * n i i e , s i t y of Kansas Czty, Kansas C i t y , Ifzssouri
Recezied J a n u a r y 16, 1944

The pendent-drop niethod of measurement of the surface tension of a liquid

has been adequately described in the liteiature. Briefly. it involves the deter-
mination of certain critical dinlensions of a drop of the liquid hanging from a suit-
able support, such as a glass capillary tip. The diniensions to be determined are
the maximum diameter of the drop, De, and the diameter, D,, of a selected cross-
1 Present address: Rescaxch L a h l a t o l i e s The 13, F Goodxicli C iixi1[1my, Aikron,0 1 ~ 0 .